Gas-to-liquid reactor and method of using

ABSTRACT

A device and a process to propagate molecular growth of hydrocarbons, either straight or branched chain structures, that naturally occur in the gas phase to a molecular size sufficient to shift the natural occurring phase to a liquid or solid state is provided. According to one embodiment, the device includes a grounded reactor vessel having a gas inlet, a liquid outlet, and an electrode within the vessel; a power supply coupled to the electrode for creating an electrostatic field within the vessel for converting the gas to a liquid and or solid state.

INCORPORATION BY REFERENCE TO RELATED APPLICATIONS

Any and all priority claims identified in the Application Data Sheet, orany correction thereto, are hereby incorporated by reference under 37CFR 1.57. This application is a continuation of PCT InternationalApplication No. PCT/US2016/049757, filed Aug. 31, 2016, which claims thebenefit of U.S. Provisional Application No. 62/214,717, filed Sep. 4,2015. Each of the aforementioned applications is incorporated byreference herein in its entirety, and each is hereby expressly made apart of this specification.

TECHNICAL FIELD

A production-worthy reactor and methods to propagate molecular growth ofhydrocarbons, either straight or branched chain structures, thatnaturally occur in the gas phase to a molecular size sufficient to shiftthe natural occurring phase to that of a liquid or solid state areprovided.

BACKGROUND

Short chain hydrocarbons exist in many species and configurations. Themost common natural occurring gaseous hydrocarbon, methane, is a singlecarbon surrounded by four hydrogen atoms. This molecule is abundantlyfound in natural gas reservoirs, generated from decaying plant andanimal matter and is a very strong greenhouse gas. The abundance, lowcost and negative environmental aspects make this gas of particularinterest in the energy, chemical processing and environmentalindustries. For example, the energy market has continuously soughtmethods to increase the value of gaseous phase hydrocarbons throughconversion to a liquid state. Likewise, specialty and fine chemicalproducers continue to seek low material cost avenues. Of equalimportance, these industries and others have sought ways to convertwaste gas streams into marketable liquid or solid products, throughchain propagation.

Many such conversion opportunities exist where venting, flaring andre-injection techniques are presently deployed. For example, vented gasfrom landfills or co-produced at crude oil production sites, flared gasat oil and gas production sites and re-injected gas sites all offerpotential economic interest. In addition the value increase fromconverting low value gas phase materials to liquid petroleum or solidcompounds to be used as products, feedstocks or potential fuels haseconomic justification. Furthermore, and as significant from anenvironmental perspective, the environmental market has sought andcontinues to seek methodologies to eliminate the venting or flaring ofgas products from landfills, bio-generation systems and waste managementsituations. Some additional areas of interest are associated withchemical processing sites, low to medium gas production sites, strandedgas situations and abandoned wells or coal bed methane and the like.Thus, opportunities arise from both economic interests and environmentalconcerns.

Numerous devices to propagate molecular chain growth in hydrocarbonshave been developed and utilized with mixed results. In the past,attention has focused on conversion based upon the Fisher-Tropschtechnology. In addition, the conversion of natural gas to hydrocarbonsby high temperature, combustion heating, pyrolysis; microwavetechnology; electromagnetic radiation; electrical discharge; the use ofa catalyst and non-catalytic oxidation techniques have been suggested.Some have suggested first heating the gas to convert a portion thereofto hydrogen and then using a catalyst to promote propagation.Specifically, patents such as U.S. Pat. No. 3,389,189, relating topyrolysis; U.S. Pat. No. 5,277,773, relating to the use of microwaves;U.S. Pat. No. 6,602,920, relating to combustion heating; U.S. Pat. Nos.7,667,085 and 7,915,463, relating to heating the gas and the use of acatalyst; and U.S. Pat. No. 8,277,631, relating to a plasma assistedelectrolytic reaction have met with mixed results especially with regardto scalability to address remote, small generation sites.

A thesis submitted to the Faculty of the Graduate College of theOklahoma State University directed to “Hydrocarbon Rearrangements andSynthesis Using an Alternating Current Silent Glow Discharge Reactor”,on file at the Oklahoma State University Library, North Boomer Annex,OSU Thesis Collection, Thesis 1993 M283h, discusses the fundamentals ofhydrocarbon pyrolysis. However, many practical problems were notresolved, such as, the efficiency of limited conversion of gas to liquidphase, nor was the utilization understood or defined. Moresignificantly, the hazardous aspects of the device disclosed in thethesis, especially in view of oil and gas industrial health and safetyconditions arising from the high voltage gradients involved in thedevice were not addressed. In addition, the possibility of an explosivereaction, and electrical shock to field personnel, as well as thelimited physical aspects of the reactor itself, all of concern in theoil and gas environment, were not addressed. Furthermore, the chemicalspecies within the liquid phase were not identified, nor were theimpacts of operating parameters to component mix or formation ratecorrelated.

SUMMARY

Although a broad range of methods for converting a gas or natural gas toa liquid are known, problems still exist with regard to the developmentof an efficient, cost effective, gas field safe, and generally safe,device and related methods for commercial industrial applications. Thedevice and the processes provided are believed to overcome the drawbacksof the known methods as well as to provide a substantial improvement inthe conversion of natural hydrocarbon gases to optionally modifiedliquid and solid phase hydrocarbons.

It is thus desirable to overcome the deficiencies of existing methods tothereby provide a device and processes for converting gaseoushydrocarbons to readily transportable upgraded liquids, such as liquidpetroleum, or solids. As used herein, a “liquid state” compriseshydrocarbons and/or modified hydrocarbons of various molecular lengths,as desired by the intended use of the liquid. As used herein, a “solidstate” comprises hydrocarbons and/or modified hydrocarbons of variousmolecular lengths, which can be selected according to the intended useof the solid. For the sake of clarity, the device and processesdisclosed herein may be utilized to generate an optionally modifiedhydrocarbon liquid having a preselected or desired vapor pressure rangeor a solid material composed of high molecular weight hydrocarbonspecies.

In addition, it is desirable to process natural gas reserves, which arecurrently not being utilized due to their location, either away from anexisting gas pipeline or isolated by the cost to build one out to thereserve. Currently, re-injection of the gas into the well, and gasflaring or venting are inefficient and wasteful dispositions of readily,available natural gas. These inefficiencies and cost-ineffective orwasteful uses are overcome by the methods and apparatus of variousembodiments.

Methods and apparatus of various embodiments can also be employed toprocess vented gas from landfills and other locations, or to reclaimand/or process chemical processing plant gas by-products, which arecurrently subjected to destruction.

In one embodiment, a device for propagating molecular growth ofhydrocarbons, either straight or branched chain structures, thatnaturally occur in the gas phases to a molecular size sufficient toshift the natural occurring phase to a liquid or solid state comprisesan electrically charged or grounded vessel having an inlet, an outletand an electrode within the vessel; and a power supply coupled throughthe vessel to the electrode.

In another embodiment, a device for converting a gas to a liquid orsolid state comprises an electrically charged or grounded vessel havingan inlet, an outlet and multiple electrodes within the vessel; and apower supply coupled through the vessel to some of the electrodes, otherof the electrodes being coupled to ground. Accordingly, the use of theterm “an electrode” encompasses multiple electrodes herein.

In another embodiment, a device for converting a gas to a liquid orsolid state comprises an electrically charged or grounded vessel havingan inlet, an outlet and an electrode within the vessel; and a variablevoltage power supply coupled through the vessel to the electrode.

In another embodiment, a device for converting a gas to a liquid orsolid state comprises an electrically charged or grounded vessel havingan inlet, an outlet and an electrode within the vessel; and a variablefrequency power supply coupled through the vessel to the electrode.

In another embodiment, a gas is subjected to an electrostatic fieldcreating a plasma for promoting molecular growth and/or converting thegas to a liquid and/or solid.

In another embodiment, a gas is subjected to an electrostatic field ofvariable frequency creating a plasma for promoting molecular growthand/or converting the gas to a liquid and/or solid.

In another embodiment, a gas is subjected to an electrostatic field ofvariable voltage creating a plasma for promoting molecular growth and/orconverting the gas to a liquid and/or solid.

Accordingly, in a generally applicable first aspect (i.e., independentlycombinable with any of the aspects or embodiments identified herein), amethod for synthesizing a liquid hydrocarbon, a solid hydrocarbon, or acombination thereof, comprising a first compound of Formula I isprovided, comprising: providing a gas phase hydrocarbon; and subjectingthe gas phase hydrocarbon to a plasma created by an electrostatic field,whereby a first compound of Formula I is produced; wherein in Formula(I), m is an integer from 0 to 40, each R¹ and R² is independentlyselected from the group consisting of hydrogen and a linear, branched,or cyclic hydrocarbon moiety of one to twenty carbon atoms, or each R¹and corresponding R² and the atoms to which they attach are joined toform a cyclic hydrocarbon moiety of 1 to 8 carbon atoms, and Z ishydrogen or methyl.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), m can be aninteger from 1 to 20.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), m can be aninteger from 5 to 8.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), each R¹ andeach R² can be independently selected from the group consisting ofhydrogen, methyl, and ethyl.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the firstcompound can be selected from butane, 2-methyl-butane, 2-methyl-pentane,n-hexane, 2,2,3-trimethyl-butane, 2-methyl-hexane, 2,3-dimethyl-Pentane,3-methyl-hexane, 2,4-dimethyl-hexane, 3,3-dimethyl-hexane,2,3,3-trimethyl-Pentane, 2,3-dimethyl-hexane, 3-methyl-heptane,2,3,5-trimethyl-hexane, 2,3,3-trimethyl-hexane, 2,3-dimethyl-Heptane,2,2,4-trimethyl-heptane, 2,4,6-trimethyl-heptane,4-ethyl-2-methyl-hexane, 2,3,5-trimethyl-heptane,2,3,6-trimethyl-heptane, and 2,3,5-trimethyl-heptane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the firstcompound can be selected from octane, 4-methyl-octane, 3-methyl-octane,2,4,6-trimethyl-octane, 4,4-dimethyl-octane, 2,5-dimethyl-octane,2,3,3-trimethyl-octane, 3,4,5,6-tetramethyl-octane,2,3,6,7-tetramethyl-octane, nonane, 3-methyl-nonane, 4-methyl-nonane,3-methyl-nonane, decane, 3,6-dimethyl-decane, 2,3,6-trimethyl-decane,and 2,5,9-trimethyl-decane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the firstcompound can be selected from undecane, 2,6-dimethyl-undecane,5,7-dimethyl-undecane, and dodecane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the firstcompound can be selected from 2,3,3-trimethyl-pentane,3,3-dimethyl-hexane, 2,3-dimethyl-hexane, 2-methyl-hexane,3-methyl-hexane, 2,4-dimethyl-hexane, 2,3-dimethyl-heptane,4-methyl-octane, 3-methyl-octane, 4,4-dimethyl octane, and3-methyl-nonane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the firstcompound can be obtained as a mixture with a second compound having thestructure of Formula (I).

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the secondcompound can be selected from Butane, 2-methyl-Butane, 2-methyl-Pentane,n-Hexane, 2,2,3-trimethyl-Butane, 2-methyl-Hexane, 2,3-dimethyl-Pentane,3-methyl-Hexane, 2,4-dimethyl-Hexane, 3,3-dimethyl-Hexane,2,3,3-trimethyl-Pentane, 2,3-dimethyl-Hexane, 3-methyl-Heptane, Octane,2,3,5-trimethyl-Hexane, 2,3,3-trimethyl-Hexane, 2,3-dimethyl-Heptane,4-methyl-Octane, 3-methyl-Octane, 2,4,6-trimethyl-Octane,2,2,4-trimethyl-Heptane, 2,4,6-trimethyl-Heptane, Nonane,4-ethyl-2-methyl-Hexane, 4,4-Dimethyl-octane, 2,3,5-trimethyl-Heptane,2,5-dimethyl-Octane, 2,3,6-trimethyl-Heptane, 2,3,5-trimethyl-Heptane,3-methyl-Nonane, 4-methyl-Nonane, 2,3,3-trimethyl-Octane, Decane,3,4,5,6-tetramethyl-Octane, 3-methyl-Nonane, 3,6-dimethyl-Decane,2,5,9-trimethyl-Decane, 2,3,6,7-tetramethyl-Octane, Undecane,2,6-dimethyl-Undecane, 5,7-dimethyl-Undecane, 2,3,6-trimethyl-Decane,and Dodecane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise condensing the liquid hydrocarbon, solidhydrocarbon, or combination thereof.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), theelectrostatic field can be an oscillating field.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the field canoscillate at a frequency from 60 to 1000 Hz.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the field canoscillate at a frequency from 300 to 600 Hz.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), theelectrostatic field can be from 1000 to 100,000 volts.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), theelectrostatic field can be from 10,000 to 50,000 volts.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), subjecting toa plasma can be conducted at ambient temperature.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), subjecting toa plasma can be conducted at a pressure from atmospheric pressure to 100PSIG.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), subjecting toa plasma can be conducted at atmospheric pressure.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the gas phasehydrocarbon can be selected from methane, ethane, n-propane, isopropane,n-butane, isobutane, ethylene, propylene, butylene, acetylene,methylacetylene, ethylacetylene, and mixtures thereof.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the gas phasehydrocarbon can be n-propane.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise isolating the liquid hydrocarbon, solidhydrocarbon, or a combination thereof.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a compound ofFormula (I) can be synthesized by the method.

In an embodiment of the first aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the compoundof Formula (I) can be substantially pure.

In a generally applicable second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a method forconverting a gas to a liquid or a solid is provided, comprising:introducing a gaseous hydrocarbon into a vessel, wherein the vessel ischarged or grounded; and subjecting the gaseous hydrocarbon to anelectrostatic field creating a plasma, whereby the gaseous hydrocarbonis converted to a liquid hydrocarbon, a solid hydrocarbon, or acombination thereof.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise subjecting the gaseous hydrocarbon to a variablefrequency electrostatic field.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise subjecting the gas to a variable voltageelectrostatic field.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise subjecting the gas to a variable frequency and avariable voltage electrostatic field.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), wherein thegaseous hydrocarbon can have a formula C_(n)H_(x)D_(y) where C iscarbon, H is hydrogen, and D is selected from the group consisting ofanother atom, a portion of a molecule, and a carbon chain, and whereinn, x, and y are each independently an integer >0.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise controlling an amount of gaseous hydrocarbonintroduced into the vessel based on a rate of conversion of the gaseoushydrocarbon to a liquid hydrocarbon, a solid hydrocarbon, or acombination thereof.

In an embodiment of the second aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the methodcan further comprise controlling an amount of gaseous hydrocarbonintroduced into the vessel based on a pressure within the vessel.

In a generally applicable third aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a method isprovided for converting a gaseous hydrocarbon to a liquid hydrocarbon, asolid hydrocarbon, or a combination thereof, substantially as describedherein.

In a generally applicable fourth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a device isprovided for converting a gaseous hydrocarbon to a liquid hydrocarbon, asolid hydrocarbon, or a combination thereof, substantially as describedherein.

In a generally applicable fifth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a liquidhydrocarbon, a solid hydrocarbon, or a combination thereof is provided,prepared using a device and/or method substantially as described herein.

In a generally applicable sixth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a fuel,adhesive, construction material, chemical treatment, solvent, coating,building block for chemical synthesis, preservative, pharmaceutical,personal care product, or refrigerant comprising a liquid hydrocarbon, asolid hydrocarbon, or a combination thereof is provided, prepared usinga device and/or method substantially as described herein.

In a generally applicable seventh aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), an isolatedliquid hydrocarbon or solid hydrocarbon prepared using a device and/ormethod substantially as described herein is provided.

In a generally applicable eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), a device forpropagating molecular growth of hydrocarbons is provided, comprising: anelectrically charged or grounded vessel having an inlet, an outlet andan electrode within the vessel; and a power supply coupled through thevessel to the electrode.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the vesselcan comprise more than one electrode.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the vesselcan comprise 1+n electrodes coupled to the power supply and n groundedelectrodes, where n is an integer >1.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the powersupply can be configured to provide a variable frequency source ofpower.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the powersupply can be configured to provide a variable voltage supply of power.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the powersupply can be configured to provide both a variable frequency supply ofpower and a variable voltage supply of power.

In an embodiment of the eighth aspect (i.e., independently combinablewith any of the aspects or embodiments identified herein), the outlet ofthe vessel can be located at a level below a liquid gas interface of thevessel.

BRIEF DESCRIPTION OF THE DRAWINGS

The details of the present disclosure, both as to its structure andoperation, may be understood in part by study of the accompanyingdrawings, in which like reference numerals refer to like parts. Thedrawings are not necessarily to scale, emphasis instead being placedupon illustrating the principles of the disclosure.

FIG. 1 is a schematic of a preferred embodiment of the device of anembodiment.

FIG. 2A is a graph showing the effect on liquid contribution of variouspower supply frequencies applied to the electrode in an embodimentaccording to Example 1.

FIG. 2B is a graph showing the effect on liquid component contributionof various power supply frequencies applied to the electrode in anembodiment according to Example 1.

FIG. 3 is a schematic plan view of the vessel 1 and the electrode 2 ofFIG. 1.

FIG. 4 is a schematic plan view of a vessel 1, as in FIG. 3; however thevessel now includes multiple electrodes 2, 3 and 4.

FIG. 5 is a cross section and top view of a reaction vessel having aparallel configuration.

FIG. 6 is a cross section and top view of a reaction vessel having aseries configuration.

FIG. 7 is a cross section and top view of a reaction vessel having alongitudinal configuration.

FIG. 8 is a cross section and top view of a reaction vessel having asolid core inner electrode.

FIG. 9 is a comparison of gas chromatogram of a product stream sample S1and solid phase sample S2 according to Example 2.

FIG. 10 is a chromatogram according to Example 1 including sample S2 andoverlays of various hydrocarbon standards. The chromatogram is shownoverlaid with a chromatogram of a sample including straight chainhydrocarbons of increasing chain length as external standards. Each peakon the standard chromatogram represents an additional carbon in thechain.

FIGS. 11A to 11D are overlays of gas chromatograms of product streamsamples S3 and S4 according to Example 2 acquired under differentchromatographic conditions.

FIGS. 12A to 12C are chromatograms of a product stream sample S4according to Example 2.

FIG. 13 is a chromatogram of a product stream sample S4 according toExample 1 compared with a chromatogram obtained from a sample ofhydrocarbon standards. The standard chromatogram includes straight chainhydrocarbons of increasing chain length as external standards. Each peakon the standard chromatogram represents an additional carbon in thechain, as indicated.

FIG. 14A and FIG. 14B are chromatograms of products stream samples S5and S6 respectively, obtained according to Example 3.

DETAILED DESCRIPTION

As used herein, “hydrocarbon” is employed to describe a moleculecontaining only carbon and hydrogen atoms. Hydrocarbons can includealkyl, alkenyl, or alkynyl groups, and can include straight or branchedchains, and acyclic or cyclic moieties. Although in preferableembodiments, liquid hydrocarbons can be present, the term “hydrocarbon”includes vapors, gases and solid materials.

The words “gas” and “short-chained hydrocarbons” are usedinterchangeably herein to describe hydrocarbons that are gases atstandard conditions (ambient temperature (20° C.) and atmosphericpressure). Such gases include but are not limited to methane (CH₄),ethane (C₂H₆), propane (C₃H₈, including isopropane and n-propane),butane (Gam, including isobutane and n-butane), ethylene (C₂H₂),propylene (C₃H₆), butylene (C₄H₈), acetylene (C₂H₂), methylacetylene,(C₃H₄), and ethylacetylene (C₄H₆).

The word “liquid” is used herein to describe such liquid hydrocarbons,as well as other petrochemical liquids that contain carbon, hydrogen,and optionally other atoms (such as O, N, S) or functional groups (suchas hydroxyls, amines, carbonyls, sulfoxides, thiols, etc.), includingmodified hydrocarbons. Generally, as provided herein, a liquid existssubstantially as a liquid at standard conditions, ambient temperature(20° C.) and atmospheric pressure. However, such a liquid may have asubstantial vapor pressure under such conditions. As provided herein, aliquid hydrocarbon and a modified hydrocarbon include those havingcyclic moieties, such as cycloalkyls, cycloalkenyls, heterocyclyls andheteroaryls. Hydrocarbons that are liquid at standard conditions(ambient temperature (20° C.) and atmospheric pressure) include but arenot limited to pentane, hexane, heptane, octane, nonane, decane, and thevarious isomers thereof (e.g., n-, iso-, sec-, tert-), as well as somecarbon-based molecules derivatized by functional groups including atomsother than carbon.

As used herein, “modified hydrocarbon” is employed to describe amolecule containing carbon atoms, hydrogen atoms, and one or moreheteroatoms.

As used herein, a “solid” comprises hydrocarbons and/or modifiedhydrocarbons as provided herein. Generally, a solid exists substantiallyas a solid at standard conditions (ambient temperature (20° C.) andatmospheric pressure). As provided herein, a solid hydrocarbon and amodified hydrocarbon include those having cyclic moieties, such ascycloalkyls, cycloalkenyls, heterocyclyls and heteroaryls.

As used herein, “alkyl” refers to a straight or branched hydrocarbonchain that includes a fully saturated (no double or triple bonds)hydrocarbon group. The alkyl group may have 1 to 20, or 1 to 40, carbonatoms (whenever it appears herein, a numerical range such as “1 to 20”refers to each integer in the given range; e.g., “1 to 20 carbon atoms”means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms,3 carbon atoms, etc., up to and including 20 carbon atoms, although thepresent definition also covers the occurrence of the term “alkyl” whereno numerical range is designated). The alkyl group may also be a mediumsize alkyl having 1 to 10 carbon atoms. The alkyl group could also be alower alkyl having 1 to 6 carbon atoms. The alkyl group of the compoundsmay be designated as “C₁-C₄ alkyl” or similar designations. By way ofexample only, “C₁-C₄ alkyl” indicates that there are one to four carbonatoms in the alkyl chain, i.e., the alkyl chain is selected from methyl,ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.Typical alkyl groups include, but are in no way limited to, methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl andhexyl. The alkyl group may be substituted or unsubstituted.

As used herein, “alkenyl” refers to an alkyl group that contains in thestraight or branched hydrocarbon chain one or more double bonds. Analkenyl group may be unsubstituted or substituted.

As used herein, “alkynyl” refers to an alkyl group that contains in thestraight or branched hydrocarbon chain one or more triple bonds. Analkynyl group may be unsubstituted or substituted.

As used herein, “cycloalkyl” refers to a completely saturated (no doubleor triple bonds) mono- or multi-cyclic hydrocarbon ring system. Whencomposed of two or more rings, the rings may be joined together in afused fashion. Cycloalkyl groups can contain 3 to 40 atoms in thering(s), 3 to 10 atoms in the ring(s) or 3 to 8 atoms in the ring(s). Acycloalkyl group may be unsubstituted or substituted. Typical cycloalkylgroups include, but are in no way limited to, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

As used herein, “cycloalkenyl” refers to a mono- or multi-cyclichydrocarbon ring system that contains one or more double bonds in atleast one ring; although, if there is more than one, the double bondscannot form a fully delocalized pi-electron system throughout all therings (otherwise the group would be “aryl,” as defined herein). Whencomposed of two or more rings, the rings may be connected together in afused fashion. A cycloalkenyl group may be unsubstituted or substituted.

As used herein, “cycloalkynyl” refers to a mono- or multi-cyclichydrocarbon ring system that contains one or more triple bonds in atleast one ring. If there is more than one triple bond, the triple bondscannot form a fully delocalized pi-electron system throughout all therings. When composed of two or more rings, the rings may be joinedtogether in a fused fashion. A cycloalkynyl group may be unsubstitutedor substituted.

As used herein, “aryl” refers to a carbocyclic (all carbon) monocyclicor multicyclic aromatic ring system (including fused ring systems wheretwo carbocyclic rings share a chemical bond) that has a fullydelocalized pi-electron system throughout all the rings. The number ofcarbon atoms in an aryl group can vary. For example, the aryl group canbe a C₆-C₁₄ aryl group, a C₆-C₁₀ aryl group, or a C₆ aryl group.Examples of aryl groups include, but are not limited to, benzene,naphthalene and azulene. An aryl group may be substituted orunsubstituted.

As used herein, “aralkyl” and “aryl(alkyl)” refer to an aryl groupconnected, as a substituent, via a lower alkylene group. The loweralkylene and aryl group of an aralkyl may be substituted orunsubstituted. Examples include but are not limited to benzyl,2-phenylalkyl, 3-phenylalkyl, and naphthylalkyl.

“Lower alkylene groups” are straight-chained —CH₂— tethering groups,forming bonds to connect molecular fragments via their terminal carbonatoms. Examples include but are not limited to methylene (—CH₂—),ethylene (—CH₂CH₂—), propylene (—CH₂CH₂CH₂—), and butylene(—CH₂CH₂CH₂CH₂—). A lower alkylene group can be substituted by replacingone or more hydrogen of the lower alkylene group with a substituent(s)listed under the definition of “substituted.”

As used herein, “heteroaryl” refers to a monocyclic or multicyclicaromatic ring system (a ring system with fully delocalized pi-electronsystem) that contain(s) one or more heteroatoms, that is, an elementother than carbon, including but not limited to, nitrogen, oxygen andsulfur. The number of atoms in the ring(s) of a heteroaryl group canvary. For example, the heteroaryl group can contain 3 to 14 atoms in thering(s), 5 to 10 atoms in the ring(s) or 5 to 6 atoms in the ring(s).Furthermore, the term “heteroaryl” includes fused ring systems where tworings, such as at least one aryl ring and at least one heteroaryl ring,or at least two heteroaryl rings, share at least one chemical bond.Examples of heteroaryl rings include, but are not limited to, thosedescribed herein and the following: furan, furazan, thiophene,benzothiophene, phthalazine, pyrrole, oxazole, benzoxazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, thiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, benzothiazole, imidazole, benzimidazole, indole,indazole, pyrazole, benzopyrazole, isoxazole, benzoisoxazole,isothiazole, triazole, benzotriazole, thiadiazole, tetrazole, pyridine,pyridazine, pyrimidine, pyrazine, purine, pteridine, quinoline,isoquinoline, quinazoline, quinoxaline, cinnoline, and triazine. Aheteroaryl group itself can, but need not be, substituted.

As used herein, “heterocyclyl” or “heteroalicyclyl” refers to amonocyclic or multicyclic ring system that contain(s) one or moreheteroatoms, that is, an element other than carbon, including but notlimited to, nitrogen, oxygen and sulfur. The number of atoms in thering(s) of a heterocyclyl group can vary. For example, the heterocyclylgroup can contain 3 to 14 atoms in the ring(s), 5 to 10 atoms in thering(s) or 5 to 6 atoms in the ring(s). A heterocycle may optionallycontain one or more double or triple bonds, but does not include a fullydelocalized pi-electron system throughout all its rings so as toconstitute a heteroaryl as provided herein. The heteroatom(s) can be anyelement other than carbon including, but not limited to, oxygen, sulfur,and nitrogen. A heterocyclyl may further contain one or more carbonyl orthiocarbonyl functionalities, so as to make the definition includeoxo-systems and thio-systems such as lactams, lactones, cyclic imides,cyclic thioimides and cyclic carbamates. When composed of two or morerings, the rings may be joined together in a fused fashion. Aheterocyclyl may include quaternized nitrogen atoms. Examples of such“heterocyclyl” or “heteroalicyclyl” groups include, but are not limitedto, those described herein and the following: 1,3-dioxin, 1,3-dioxane,1,4-dioxane, 1,2-dioxolane, 1,3-dioxolane, 1,4-dioxolane, 1,3-oxathiane,1,4-oxathiin, 1,3-oxathiolane, 1,3-dithiole, 1,3-dithiolane,1,4-oxathiane, tetrahydro-1,4-thiazine, 1,3-thiazinane, 2H-1,2-oxazine,maleimide, succinimide, barbituric acid, thiobarbituric acid,dioxopiperazine, hydantoin, dihydrouracil, trioxane,hexahydro-1,3,5-triazine, imidazoline, imidazolidine, isoxazoline,isoxazolidine, oxazoline, oxazolidine, oxazolidinone, thiazoline,thiazolidine, morpholine, oxirane, piperidine N-Oxide, piperidine,piperazine, pyrrolidine, pyrrolidone, pyrrolidione, 4-piperidone,pyrazoline, pyrazolidine, 2-oxopyrrolidine, tetrahydropyran, 4H-pyran,tetrahydrothiopyran, thiamorpholine, thiamorpholine sulfoxide,thiamorpholine sulfone, and their benzo-fused analogs (e.g.,benzimidazolidinone, tetrahydroquinoline, and 3,4-methylenedioxyphenyl).A heterocyclyl group itself can, but need not be, substituted.

The various molecules and groups as described herein can be converted orproduced or propagated in methods of various embodiments. The words“propagation” as applied to molecular growth of hydrocarbons, modifiedhydrocarbons, and solid phase hydrocarbons and “converting” a gas to aliquid or solid are also used interchangeably herein.

In a preferred embodiment, a device is provided for propagatingmolecular growth of hydrocarbons, either straight or branched chainstructures, that naturally occur in the gas phase to a molecular sizesufficient to shift the natural occurring phase to a liquid or solidstate comprises a vessel having an inlet, an outlet and an electrodewithin the vessel; and a power supply coupled through the vessel to theelectrode, which propagates the molecular growth of hydrocarbons. Thepower supply is coupled to the electrode such that an electric field isinduced within the vessel which creates a plasma in the gas within thevessel wherein propagation to the liquid and solid phase can beinitiated and maintained. As such, low to moderate pressures within thevessel are maintained, e.g., atmospheric or less to 100 PSIG or more,wherein a preferred range is atmospheric to 5, 10, 15, 25, 50, or 75PSIG. In addition, it is believed that the electrostatic induced plasmaexcites electrons in the electron cloud of the gas molecule andminimizes the energy transfer to the nucleus of the gas phase molecules.This hypothesis is supported in that it is has been found that theprocess causes little, if any, temperature rise in the gas itself or inthe liquid downstream of the reaction chamber. Accordingly, the processcan be conducted at outdoor ambient temperatures, e.g., −90° C. to 58°C., or higher or lower temperatures, as desired, although temperaturesare desirably controlled so as to obtain a desired product in liquid orsolid form. Generally, as pressure increases, collisions of moleculesand ions will increase. Without wishing to be limited by theory, it ishypothesized that higher pressures may enhance propagation rate, and/orabsolute molecular size due to propagation. In some embodiments,pressure may be selected to be sufficient to overcome open line flowresistance. In some embodiments, pressure can be about 200 PSIG, 300PSIG, 400 PSIG, 500 PSIG, 1000 PSIG, 2500 PSIG, 5000 PSIG, or valuesthere between. In certain embodiments, subjecting to a plasma can beconducted at a pressure from atmospheric pressure to 100 PSIG. Infurther embodiments, subjecting to a plasma can be conducted atatmospheric pressure.

FIG. 1 is a schematic of a preferred embodiment of the device 100. Thedevice 100 is comprised of an annular reaction chamber or vessel 1 ofthe type found in oil or gas process, and can be fabricated to complywith the AMSE Code for Pressure Vessels, Section VIII. While an annularreaction chamber can advantageously be employed, other reaction chamberconfigurations can also be employed in certain embodiments. These caninclude multi-tube systems, parallel plate systems, honeycombconfigurations, cylindrical, spherical, or any other desiredconfiguration. Because the process can advantageously be conducted atlower pressures and temperatures, flexibility in reactor configurationcan be achieved. In one embodiment, the vessel is fabricated so as tofit a standard shipping pallet size so as to facilitate transport toremote locations, and additional components of the system can bedesigned to assemble in a modular fashion on site.

The vessel includes at least one electrode 2, also called a poweredelectrode herein to refer to an electrode to which an electrical powersource is coupled; gas inlet 12, which is coupled on its upstream sideto the gas phase feed, which can be sourced from natural gas reserve oranother supply (not shown); a liquid outlet 30, which is coupled on itsdownstream side to the liquid or product collection unit (not shown);and a power supply 8 coupled to the electrode 2. The electrodes employedcan be those commercially available for use in plasma generatingsystems, or can be specifically configured to the reactor and conditionsencountered in the process application.

The power supply 8, more fully described below, provides power to theelectrode 2 in the form of an application voltage of 1,000 to 100,000volts alternating current, at a frequency range of 60 to 1,000 Hz,wherein it has been found that voltages of approximately 24.6 KVAC(24,600 VAC) at approximately 440 Hz, and 20,000 VAC at approximately300 Hz, are preferred. The power supply 8, if it does not supply its ownpower, is connected to external or operational input power source at theparticular site. External power supplies with voltages of 110/115,208/220/240 or 440 VAC in either, possibly in the form of a 440 volt,single or three phase source supply and frequencies of 50 or 60 Hz aswell as other combinations can be utilized. In that event, the powersupply takes the external or operational input power and modifies thevoltage and frequency as required, as further explained herein. Thepower supply 8 is coupled to the electrode 2 via a high voltage cable11, through the reaction vessel entrance 6 and high voltage insulatorentrance bushing 4. In a preferred embodiment, the external surface ofthe reaction chamber 1 is maintained at ground potential, zero voltage,via the reaction chamber ground connection 7. The reaction chamberground connection 7 is designed to function as a primary ground pathwayto ensure elimination of electrical potential on the exterior of thereaction chamber 1. The power supplied to the electrode 2 creates anelectric field in the gas region or plasma zone 13, see FIG. 1 and FIG.3, located within the vessel 1 between the electrode 2 and the vessel 1,it being understood that the vessel 1 is at ground potential. Asecondary ground pathway is provided by the hard piped confirmation tothe gas feed source and liquid product outlet, that is, the piping beinggrounded, for example at 50 and 55, also provides an additionalsafeguard. In locations where liquid fuel (e.g., diesel fuel), gaseousfuel (e.g., natural gas or propane) or electricity are readilyavailable, these can be employed to provide energy to the power supply,e.g., through the use of diesel or natural gas generators, or solar cellsystems. In remote locations, it can be desirable to supply energy tothe power supply via combustion of a portion of the gaseous hydrocarbonsand to subject a remaining portion of the gaseous hydrocarbons toconversion, or to retain a portion of the liquid hydrocarbons producedto employ as a fuel for a generator. Other apparatus and methods forgenerating electricity can be employed or adapted to supply energy tothe power supply. In some embodiments, device 100 need not operate as anelectrically grounded system. In certain embodiments, the electrode 2and vessel 1 can be maintained at a voltage above ground potential. Forexample, if a multiphase, such as a 3 phase, power source is employed,it may be advantageous to connect electrode 2 and/or vessel 1, to phasesof the power supply 8. In such embodiments, the ground 7 would bereplaced by electrical connection to an appropriate phase of powersupply 8. In some embodiments, the voltage can be from about 1000 to100,000 volts, from about 10,000 to 50,000 volts AC, from about 20,000to 30,000 volts AC, from about 24,000 to 26,000 volts AC. In certainembodiments, field can oscillate at a frequency from 60 to 1000 Hz orfrom 300 to 600 Hz.

The frequency of the applied voltage may be tuned depending on the sizeof the vessel 1, the gas feed composition and the targeted product vaporpressure range. Without wishing to be limited by theory, it is believedthat the frequency of the applied voltage should be selected tocorrespond to the capacitance of vessel 1. The capacitance of vessel 1,along with other components of the power circuit, may provide aparticular resonance frequency.

The power supply 8 is a unit that is able to provide power of bothvariable frequency and variable alternating current voltage potential tothe electrode 2. The power supplied to the electrode 2 is modified byadjusting the voltage potential or by modifying the frequency thereof orboth to create the desired gas to liquid or solid conversion rate and/orliquid component distribution required by the user. The alternatingpotential change, or variable frequency, is manipulated at the powersupply 8 and adjusted to maximize the gas to liquid or solid conversionrates for various inlet feed streams or for various outlet liquidhydrocarbons and/or modified hydrocarbons, and/or solid phasehydrocarbons as further described herein. As such, an alternatingcurrent of variable potential and or variable frequency is applied tothe electrode 2 through entrance bushing 4 located in the liquid phaseor liquid collection region 16 of the vessel 1. The power supply 8 iscapable of modifying both the frequency and voltage supplied in responseto the conversion process and in this way optimum conversion of specifichydrocarbons may be obtained. In addition as the feed gas molecularstructure may not be constant, such that adjustment of frequency orvoltage or both supplied to the electrode 2 is beneficial to thepropagation of the molecular hydrocarbons of interest. Apparatus forcontrolling frequency and voltage of energy provided by a power supplyare commercially available. Input from sensors within the system, e.g.,of liquid level, of temperature, of pressure, of hydrocarbon and/ormodified hydrocarbon composition (e.g., IR detectors, gaschromatography, mass spectrometry, conductivity), or the like can beprocessed by a microprocessor or other computer or computing system andcan be employed to adjust frequency and voltage, the flow rate ofgaseous components into the reactor, or other operating conditions.

In certain embodiments, a particular wave form of the energy isselected. The wave form may have a significant impact on the reactionkinetics and/or production composition. Suitable wave forms include, butare not limited to, square waves, triangle waves, sawtooth waves, pulsedwaves and/or superimposed waves, e.g., a plurality of high frequencywaves that collectively form a square or sinusoidal wave, or acombination of the foregoing. In liquid coalescence applications, e.g.,coalescence of water, it is observed that a superimposed ormulti-component wave form can greatly enhance coalescence rates. Anotheroption for adjusting, e.g., reaction kinetics and/or productioncomposition, in the power cycle is pulsed (off/on) duties. Thefragmentation and chain propagation may be enhanced by pulsing theon/off cycles with a preset timing. The on/off cycle may be at afrequency greater than, the same as, or less than a frequency of thesupply power. The on cycle frequency may be independent of the on/offcycle. For example, an on/off cycle frequency lower than the highvoltage frequency may be employed, e.g., the on/off cycle is establishedat 100 times per second with the power frequency at 500 Hz.Alternatively, the on/off cycle frequency is higher than the highvoltage frequency, e.g., the on/off cycle established at 500 times persecond with the high voltage frequency at 350 Hz.

The electrode 2 is preferably covered with an insulating material, e.g.,glass or ceramic, with dielectric properties capable of supportingplasma formation and physical properties able to survive the internalconditions of the reactor vessel 1 for commercial use. Quartz was foundto be a material suitable for the electrode covering, however, any othersuitable material may also be employed. Certain materials, e.g.,ceramics, can potentially be catalytic in nature. For example, certainoxide ceramics can act as catalytic surfaces in hydrocarbon reactions.Thermal pyrolysis has utilized various catalytic materials to promotesuch reactions. Accordingly, the insulating material can be selected forcatalytic properties or an absence of catalytic properties, dependingupon the intended feedstock and product stream. In various embodiments,the electrode 2 is coated with a material selected from a glass, aceramic, such as an oxide such as an alumina, beryllia, ceria, orzirconia, a nitride, a boride, a silicide, or a carbide. In someembodiments, a ceramic can be selected from barium titanate, boronoxide, boron nitride, ferrite, lead zirconate titanate, magnesiumdiboride, porcelain, silicon aluminum oxynitride, silicon carbide,silicon nitride, magnesium silicate, titanium carbide, yttrium bariumcopper oxide, zinc oxide, or zirconium oxide. A ceramic material can becrystalline or amorphous.

Control of various components of the devices of the embodiments may bedistributed at the various components, for example, control of the powersupply, specifically the frequency, the voltage, and on or off power canbe manipulated at the power supply. In addition, as the gas within thevessel 1 is converted to liquid or solid within the reactor vessel 1,the volume of liquid or solid increases and the volume of gas, thedirect correlation to pressure, decreases, the gas inlet feed rate isheld equal to the liquid production rate. Accordingly, internal vesselpressure may be controlled by simply controlling the gas feed flow rate,that is, by operation, increasing or decreasing the opening of the flowvalve. On site control may advantageously be employed; alternatively,remote control by use of satellite or cellular technology may also beemployed.

Numerous controls or combinations of controls may be manipulated byindividuals and/or various centralized control systems can beimplemented. In this regard, a master control unit or master controller9, which may be a programmable logic controller, a PC based system orconnected into a distributed control system as is known in the art, iscoupled to: the vessel pressure indicator 32 via a pressure controller14 coupled to a gas inlet 12, via a gas feed control valve 15; liquidoutlet 30 via a liquid outlet flow measurement device 10; an emergencyisolation valve 21 and an emergency isolation valve 22; a safety reliefsensor 20 coupled to a safety relief device or pressure relief device 19attached to the vessel 1 as commonly used in the industry; a liquidlevel control device 17, coupled to a liquid control valve 18; and tothe power supply 8. The master control unit 9 is able to adjust theelectrical potential, or the potential change, or frequency or anycombination thereof to the electrode 2 to optimize the conversion rateof gas to liquid or solid. It is also feasible to manipulate theparameters to optimize a particular vapor pressure range, ordistribution of compounds, in the product as required by the user. Theoperation of the system is designed to maximize efficiency by allowingthe gas to liquid/solid conversion rate to act as the control basis. Asthe gas is converted to liquid or solid within the reactor, the volumeof liquid or solid increases and the volume of gas, the directcorrelation to pressure, decreases. Under this scenario, the gas inletfeed rate will be held equal to the liquid or solid formation and/orproduction rate. In case of excessive pressure rise, for example,pressure approaching the maximum allowable working pressure (MAWP) ofthe vessel, the pressure relief valve 19 will respond to release thepressure, a high pressure alarm, integrated into the mater controller 9,will activate, the flow sensor will detect the pressure release flow andthe master control unit 9 will respond to the flow sensor 20 to closethe emergency feed shut off or isolation valve 21 and de-energize thepower supply 8. Mass balance is controlled by outlet flow rate and thepressure variable. As such, the interactions between liquid or solidformation and gas conversion can be used to control the internalpressure and flow rate simultaneously. With this basis, the inlet flowrate is dependent on the internal pressure and the outlet product ratecan then be used to optimize the conversion rate. That is, the outletflow rate is measured and the setting of voltage and frequency optimizedto maximize the outlet flow rate (highest conversion). The pressure inthe vessel will decrease as the gas is converted to the liquid and/orsolid phase. The pressure is then maintained in the vessel by allowingmore feed gas into the vessel. Therefore, the inlet flow rate isdependent on the pressure while the pressure will decrease directlyproportional with the conversion, or the outlet flow rate.

The frequency and secondary voltage can be manipulated by the mastercontrol based on the liquid product flow rate, or solid production rate.The product flow meter 10 inputs the liquid outlet rates to the mastercontroller. The frequency and secondary voltage are manipulated by themaster controller 9 to optimize the process, such manipulation of thecontrolled variables in response to other measurements is wellunderstood for example via a fuzzy logic algorithm. It is understoodthat the frequency and voltage can also be set by the user and notmanipulated such that the process proceeds based on mass balance alone.

With regard to the conversion of liquid, referring for example to FIGS.11A through 11D, the liquid component can be comprised of numeroushydrocarbon species which can contain both straight and branched chainconfigurations. TABLE 1 represents a component analysis of liquid phasematerial of an embodiment according to Example 2, below.

Depending upon the nature of the feedstock, sulfur and/or oxygencontaining species, modified hydrocarbons as provided herein, may bepresent in the product stream in addition to hydrocarbon products.Operating parameters may be adjusted to shift production preferentiallyto selected sulfur and/or oxygen products, e.g., for ease of subsequentremoval, or to minimize production of the most detrimental species.

The product stream may contain molecules including any atom or set ofatoms, so long as the constituent atoms can be present in the feedstock.In addition to atoms mentioned above, the product stream may includemolecules that contain one or more of pnictogens, such as nitrogen,chalcogens, such as oxygen and sulfur, halogens, such as fluorine,chlorine, bromine and iodine, and metals, such as sodium and titanium,or semi-metals, such as boron and silicon. The product stream mayinclude molecules having functional groups including the aforementionedatoms. In various embodiments, molecules in a product stream may includefunctionalities such as, for example, alcohols, ethers, ketones,aldehydes, carboxylic moieties such as acids and esters, carbonates,sulfides, sulfones, amines, amides, carbamates, nitros, oximes,peroxides, hydrazines, and other functionalities familiar to those ofskill in the art.

In some embodiments, a product stream can include a modifiedhydrocarbon. A modified hydrocarbon as provided herein includes a liquidor solid hydrocarbon in which one or more hydrogen atoms is replaced bya heteroatom. Modified hydrocarbons include those in which a ring isformed by the heteroatom, for example, to constitute a heteroaryl and/orheterocyclyl as provided herein. For example, methylamine is defined asa modified methane, while benzoic acid is defined as a modified toluene.The heteroatom that replaces a hydrogen atom can be any suitableheteroatom provided herein. When including one or more double bonds, amodified hydrocarbon as provided herein is interpreted to include alltautomeric forms.

The product stream can include a liquid or solid hydrocarbon modifiedwith any suitable substituent. For example, a modified hydrocarbon caninclude one or more of alkoxy, cycloalkyl, cycloalkenyl, acylalkyl,alkoxyalkyl, aminoalkyl, amino acid, aryl, heteroaryl, heterocyclyl,aryl(alkyl), heteroaryl(alkyl), heterocyclyl(alkyl), hydroxy,hydroxyalkyl, acyl, cyano, halogen, thiocarbonyl, O-carbamyl,N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido,S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato,thiocyanato, isothiocyanato, azido, nitro, silyl, sulfenyl, sulfinyl,sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl,trihalomethanesulfonamido, amino, mono-substituted amino, di-substitutedamino, boronic acid, or ferrocene as those terms are understood by thoseof skill in the art. Heteroaryl substituents include, but are notlimited to imidazoles, furans, thiophenes, pyrroles, pyrimidines,pyrazines, pyridines, pyrazoles, oxazoles, isoxazoles, benzothiophenes,benzofurans, indoles, quinolines, isoquinolines, benzooxazoles,benzoisoxazoles, benzoisothiazoles, benzothiazoles, benzoimidazoles,benzotriazoles, 1H-indazoles, and 2H-indazoles.

The feedstock(s) and mixed component feed materials may be introducedinto the reactor at any suitable temperature, e.g., below, at, or aboveambient temperature. It can be advantageous to heat the feedstock priorto introducing it into the reaction chamber, so as to ensure that thelarger chain hydrocarbons remain in the gas phase as the feedstockenters the plasma zone. The weaker bond strengths of larger chainhydrocarbons may be a driver for carbonyl radical formation that attacksthe smaller, stronger bond species. This alternative mode of operationenables shifting the phase of normal state liquids to gas/vapor forhomogeneous feed into the reactor. An acceleration in the reaction isalso possible by comingling various gas phase hydrocarbons with theprimary methane/natural gas source. This co-mingling process may lowerthe total energy requirement to establish and maintain the fullydeveloped plasma and/or allow product manipulation through co-minglingadjustment. Using higher chain hydrocarbons may increase the ionizationand radical formation to drive propagation to components that exist inthe liquid or solid phase. In some embodiments, subjecting to a plasmacan be conducted at ambient temperature.

To assist the condensation of the propagated hydrocarbon chains, amechanical device or component in the non-plasma area above or below theplasma reaction zone(s) may be employed. Such a device can be one ormore of the types of “demister” materials or apparatus used inconventional liquid/gas separation processes. This configuration canassist in the collection of vapor phase components on the surface tosupport liquid droplet formation and liquid collection.

Distillation is the process of separating components based on the vaporpressure of the materials. Major petroleum products are categorized intobroad groups based on the product take off location, or vapor pressurerange, in the distillation process. Products are generally categorizedas Light, Middle or Heavy Distillates. Light distillates typicallycontain hydrocarbons used in gasoline, kerosene and jet fuel. Middledistillates typically contain hydrocarbons used in diesel fuels, heatingoil and other light oil applications. Heavy distillates containhydrocarbons typically used in heavy fuel oils or other heavy oilapplications. As such, specific molecular components are not isolated inthese valuable products. Therefore, the products resulting from thechain propagation process do not require isolation prior to consumptionor additional processing. However, in some embodiments, product streamcomponents may be separated and/or purified as provided herein.

In this regard, the user of the device 100 having a variable frequencypower supply 8, may manipulate the liquid/solid component distribution,that is the molecular chains, to be collected, used or otherwisedisposed by changing the frequency of the power supplied to theelectrode 2. More specifically, by controlling the power to theelectrode, varying the frequency or voltage or both, propagation ofliquid/solid hydrocarbons of the type, C_(n)H_(x)D_(y), where C iscarbon, H is hydrogen and D is another atom, molecule or carbon chain,and n, x and y are the numbers associated with each. Accordingly,various liquid/solid hydrocarbons may be propagated through this processand specific product categories, as defined by their vapor pressurerange, may be targeted to be produced as necessary or required.

In some embodiments, a liquid hydrocarbon or a solid hydrocarbonprovided herein can have the structure of Formula I:

wherein m can be an integer from 0 to 40, each R¹ and R² canindependently be hydrogen or a linear, branched, and/or cyclichydrocarbon moiety of one to twenty carbon atoms, or each R¹ andcorresponding R² and the atoms to which they attach can be joined toform a cyclic hydrocarbon moiety of 1 to 8 carbon atoms, and Z can behydrogen or methyl. In some embodiments, each R¹ and R² may beindependently selected from a C₁₋₈ alkyl, a C₁₋₈ alkenyl, and a C₁₋₈alkynyl. In some embodiments, each R¹ and R² can independently have thestructure of Formula (II):

wherein m^(A) can be an integer from 0 to 8, and each R^(1A) and R^(2A)can independently be chosen from hydrogen, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, pentyl, 2-methyl butyl, 3-methylbutyl, 2-ethyl propyl, hexyl, 2-methyl pentyl, 3-methyl pentyl, 4-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, and cyclodecyl. Each R^(1A) and R^(2A) can independently bethe same or different as any other R^(1A) or R^(2A). Preferably, m^(A)can be an integer from 0 to 2. Preferably, each R^(1A) and R^(2A) canindependently be hydrogen or methyl. Examples of compounds of Formula(I) include, but are not limited, to butane, 2-methyl-butane,2-methyl-pentane, n-hexane, 2,2,3-trimethyl-butane, 2-methyl-hexane,2,3-dimethyl-pentane, 3-methyl-hexane, 2,4-dimethyl-hexane,3,3-dimethyl-hexane, 2,3,3-trimethyl-pentane, 2,3-dimethyl-hexane,3-methyl-heptane, 2,3,5-trimethyl-hexane, 2,3,3-trimethyl-hexane,2,3-dimethyl-heptane, 2,2,4-trimethyl-heptane, 2,4,6-trimethyl-heptane,4-ethyl-2-methyl-hexane, 2,3,5-trimethyl-heptane,2,3,6-trimethyl-heptane, 2,3,5-trimethyl-heptane, octane,4-methyl-octane, 3-methyl-octane, 2,4,6-trimethyl-octane,4,4-dimethyl-octane, 2,5-dimethyl-octane, 2,3,3-trimethyl-octane,3,4,5,6-tetramethyl-octane, 2,3,6,7-tetramethyl-octane, nonane,3-methyl-nonane, 4-methyl-nonane, 3-methyl-nonane, decane,3,6-dimethyl-decane, 2,3,6-trimethyl-decane, 2,5,9-trimethyl-decane,undecane, 2,6-dimethyl-undecane, 5,7-dimethyl-undecane, dodecane,2,3,3-trimethyl-pentane, 3,3-dimethyl-hexane, 2,3-dimethyl-heptane,4-methyl-octane, 3-methyl-octane, and 3-methyl-nonane.

In some embodiments, a compound of Formula (I) can be obtained as amixture with a second, different, compound of Formula (I).

In some embodiments, the second compound is selected from the groupconsisting of Butane, 2-methyl-Butane, Acetone, Isopropyl Alcohol,2-methyl-Pentane, n-Hexane, 2,2,3-trimethyl-Butane, 2-methyl-Hexane,2,3-dimethyl-Pentane, 3-methyl-Hexane, 2,4-dimethyl-Hexane,3,3-dimethyl-Hexane, 2,3,3-trimethyl-Pentane, 2,3-dimethyl-Hexane,3-methyl-Heptane, Octane, 2,3,5-trimethyl-Hexane,2,3,3-trimethyl-Hexane, 2,3-dimethyl-Heptane, 4-methyl-Octane,3-methyl-Octane, 2,4,6-trimethyl-Octane, 2,2,4-trimethyl-Heptane,2,4,6-trimethyl-Heptane, Nonane, 4-ethyl-2-methyl-Hexane,4,4-Dimethyl-octane, 2,3,5-trimethyl-Heptane, 2,5-dimethyl-Octane,2,3,6-trimethyl-Heptane, 2,3,5-trimethyl-Heptane, 3-methyl-Nonane,4-methyl-Nonane, 2,3,3-trimethyl-Octane, Decane,3,4,5,6-tetramethyl-Octane, 3-methyl-Nonane, 3,6-dimethyl-Decane,2,5,9-trimethyl-Decane, 2,3,6,7-tetramethyl-Octane, Undecane,2,6-dimethyl-Undecane, 5,7-dimethyl-Undecane, 2,3,6-trimethyl-Decane,and Dodecane.

In some embodiments, a liquid hydrocarbon, solid hydrocarbon, orcombination thereof is condensed.

In some embodiments, each R¹ and R² can independently be chosen fromhydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,pentyl, 2-methyl butyl, 3-methyl butyl, 2-ethyl propyl, hexyl, 2-methylpentyl, 3-methyl pentyl, 4-methyl pentyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Each R¹ and R² canindependently be the same or different as any other R¹ or R². In someembodiments, m can be an integer from 1 to 20, from 20 to 40, from 1 to12, from 1 to 8, from 3 to 8, from 3 to 7, from 4 to 7, from 4 to 8,from 5 to 7, or from 5 to 8.

Input to the master controller 9 from the product outlet flow rate viathe outlet flow measurement device 10 is a measured dependent variable.The independent variables of potential and frequency are optimized tomaximize the conversion rate. The gas feed inlet rate is a dependentvariable in direct proportion to the gas to liquid conversion rate thatis a direct correlation of the outlet product flow rate. Simply stated,the mass flow rate of the gas feed stream through the inlet 12 is equalto the measured liquid product outlet with a constant vessel pressure.

The high voltage entrance bushing 4 is of the type typically used inhigh voltage, electrostatic dehydration and desalination processescommon to the oil and gas industry. Established oil field equipmentcompanies have successfully utilized high voltage in processapplications for many years. In addition, it is noted that the entrancebushing 4 is preferably located in the region of the vessel 1 in whichthe liquid phase is collected, that is, the liquid phase region orcollection area 16. The interface between the liquid and the gas or theliquid level is shown as broken line 5 in FIG. 1.

The liquid level 5, within the liquid phase region 16 is controlled bythe liquid level controller 17 that manipulates the liquid control valve18. The liquid level is maintained for two functions: (1) to create adiscrete plasma zone end plane at one end of the reaction chamber 1; and(2) to protect the high voltage entrance bushing 4 from corona attackand deterioration caused by the plasma phase reaction(s). The liquidlevel 5, and plasma zone interface may be initially established bycharging a volume of hydrocarbon liquid, oil or solvent into the vessel1. This initial charge establishes the liquid-plasma boundary andprovides the liquid level protection for the entrance bushing 4.

The safety relief device 19 is located on the reaction chamber 1, abovethe active plasma reaction zone, to ensure that overpressure scenariosare mitigated, for example, prior to the vessel pressure reaching themaximum allowable working pressure (MAWP) of the reaction chamber 1. Inthis regard, the emergency relief sensor 20 detects flow through theemergency relief device 19 and signals the master controller 9 whichdisengages the power supply 8 and closes the reaction chamber gas feedinlet via emergency isolation inlet valve 21 and closes the productoutlet via emergency isolation outlet valve 22. In this way, thereaction chamber 1 is de-energized and inlet 12 and outlet 30 areisolated from material flow.

In operation, hydrocarbon gas is fed into the reaction chamber 1 throughthe reaction chamber gas inlet 12. The reaction chamber gas inlet 12 islocated above the gas-liquid interface 5 to maximize retention time inthe plasma zone 13 and drive conversion to the liquid or solid phase.The power supplied to the electrode 2 initiates a plasma within the gasin the vessel 1 in plasma zone 13 causing the propagation of the gas toa molecular size sufficient to shift the phase to a liquid or solid. Thegas feed rate into the reaction chamber 1 through the reaction chamberinlet 12 is controlled by the reaction chamber pressure controller 14via the gas feed inlet control valve 15. The reaction chamber pressurecontroller 14 is coupled to a gas pressure sensor 32. The reactionchamber pressure is maintained within a narrow operating range byallowing gas to flow into the reaction chamber 1 via the feed gascontrol valve 15 at a mass rate equal to the product outlet rategoverned by the conversion from gas to liquid/solid.

It is well known that at a particular voltage there is a physical limitto the gap between the electrode and the ground plane to which a plasmazone 13 can be created. This physical restriction in gap size limits thereaction volume of a specific height vessel. One manner to increase theeffective reaction volume, while maintaining an effective electricalgradient between the electrode and the ground plane, and withoutsignificantly increasing the overall height of the system 100, andwithout increasing the voltage is to use multiple electrodes. Referringto FIG. 3, the vessel 1, the electrode 2, and plasma zone 13 of FIG. 1are shown in schematic plan view. Now referring to FIG. 4, the internalplasma reaction volume of the vessel 1 may be increased withoutincreasing the height of the vessel by the addition of one or morepowered electrodes and a corresponding one or more grounded electrodescreating additional plasma zones. As shown in FIG. 4, which again is aschematic plan view of the device 100, the vessel 1 includes multipleelectrodes 42, 43, and 44. In this embodiment, a further poweredelectrode 43 is located within the vessel 1 disposed about the poweredelectrode 42, which corresponds to electrode 2 in FIG. 1 and FIG. 3. Inaddition, a grounded electrode 44 is disposed about electrode 42 andbetween electrodes 42 and 43. In this way plasma zone 413, similar toplasma zone 13 of FIG. 1 and FIG. 3, is formed between the electrode 43and the vessel wall. More importantly, additional plasma zones 414 and415 are formed between the ground electrode 44 and powered electrode 43and ground electrode 44 and powered electrode 42 respectively, therebyincreasing the total effective reaction volume of the device whichthereby increases the gas to liquid/solid conversion rate as compared tothe internal volume of the single electrode of the vessel 1 of FIG. 1and FIG. 3.

Various configurations can be employed for the reaction vessel. Parallelconfigurations (e.g., FIG. 5) enable flow to enter several plasma zonessimultaneously. In a series configuration (e.g., FIG. 6), flow passesthrough sequential plasma zones. Each zone can be the same or different,e.g., having different voltage and/or frequency and/or length. In alongitudinal configuration (e.g., FIG. 7), long, thin plasma zones areformed with free gas gaps between the plasma zones, so as to facilitatefree gas to plasma zone interface reactions. In a solid core innerelectrode configuration (e.g., FIG. 8), a reactor having a solid coreelectrode and an insulated outer grounded vessel wall is employed. Sucha simple configuration may offer advantages in ease of maintenanceand/or reduced manufacturing expense.

While not wishing to be bound by theory, it is believed that the highestchain propagation may exist at the gas phase/plasma interface and notwithin the plasma itself. As the hydrocarbon chain increases, the energylevel required to fracture the carbon-carbon bonds and/orcarbon-hydrogen bonds decreases. Accordingly, as the concentration ofhigher chain species increases, the reaction would reach an equilibriumof fracturing and recombining of the larger molecules. The energy isreadily absorbed in the high chain species and the smaller higher bondenergy species become less fractured or form fewer radicals in theequilibrium state. To shift the equilibrium further toward increasedpropagation rates, a balance of radical formation using the smallerchain species is desired. Accordingly, formation of aggressive radicalsthat attack non-fragmented molecules is desirable. One example of aninterface configuration expected to facilitate this process involvesthin plasma zones along the longitudinal direction of the reactor withfree gas space between the longitudinal plasma zones, e.g., as depictedin FIG. 7.

Alternatively, the mechanism promoting propagation may be related to theionized gas, solid material interface that forms along the wettedsurface of the plasma zone 13. As such, an embodiment designed tomaximize this interfacial area may be employed to enhance propagationrates.

Generally, a product stream produced by the methods or devices providedherein will include a plurality of hydrocarbons and/or modifiedhydrocarbons. A product stream can include only hydrocarbons, caninclude only modified hydrocarbons, or can include a mixture ofhydrocarbons and modified hydrocarbons. A liquid or solid hydrocarbon ormodified hydrocarbon can be any compound prepared by the methods anddevices provided herein, for example, those named in Weissermel K. etal., Industrial Organic Chemistry, 3rd, Completely Revised Edition(Wiley, 2008). A liquid or solid hydrocarbon or modified hydrocarbonproduced by the methods or devices provided herein may have thestructure of Formula (I), as provided herein. Such compounds may beselected from, but are not limited to, those provided in Table 1.

TABLE 1 IUPAC Chemical Name Chemical Formula Propane C3H8 IsobutaneC4H10 Butane C4H10 Butane, 2-methyl- C5H12 Acetone C3H6O IsopropylAlcohol C3H8O Pentane, 2-methyl- C6H14 n-Hexane C6H14 Butane,2,2,3-trimethyl- C7H16 Hexane, 2-methyl- C7H16 Pentane, 2,3-dimethyl-C7H16 Hexane, 3-methyl- C7H16 Hexane, 2,4-dimethyl- C8H18 Hexane,3,3-dimethyl- C8H18 Pentane, 2,3,3-trimethyl- C8H18 Hexane,2,3-dimethyl- C8H18 Heptane, 3-methyl- C8H18 Octane C8H18 Hexane,2,3,5-trimethyl- C9H20 Hexane, 2,3,3-trimethyl- C9H20 Heptane,2,3-dimethyl- C9H20 Octane, 4-methyl- C9H20 Octane, 3-methyl- C9H20Octane, 2,4,6-trimethyl- C11H24 Heptane, 2,2,4-trimethyl- C10H22Heptane, 2,4,6-trimethyl- C10H22 Nonane C9H20 Hexane, 4-ethyl-2-methyl-C9H20 4,4-Dimethyl octane C10H22 Heptane, 2,3,5-trimethyl- C10H22Octane, 2,5-dimethyl- C10H22 Heptane, 2,3,6-trimethyl C10H22 Heptane,2,3,5-trimethyl- C10H22 Nonane, 3-methyl- C10H22 Nonane, 4-methyl C11H24Octane, 2,3,3-trimethyl- C11H24 Decane C10H22 Octane,3,4,5,6-tetramethyl- C12H26 Nonane, 3-methyl- C10H22 Decane,3,6-dimethyl- C12H26 Decane, 2,5,9-trimethyl- C13H28 Octane,2,3,6,7-tetramethyl- C12H26 Undecane C11H24 Undecane, 2,6-dimethyl-C13H28 Undecane, 5,7-dimethyl- C13H28 Decane, 2,3,6-trimethyl- C13H28Dodecane C12H26

In certain embodiments, a liquid or solid hydrocarbon or modifiedhydrocarbon as provided herein may be characterized by its degree ofunsaturation. For example, a liquid or solid hydrocarbon or modifiedhydrocarbon can have one degree of unsaturation, two degrees ofunsaturation, three degrees of unsaturation, four degrees ofunsaturation, five degrees of unsaturation, or more. In otherembodiments, a liquid or solid hydrocarbon or modified hydrocarbon asprovided herein can be characterized by the included number of rings.For example, a liquid or solid hydrocarbon or modified hydrocarbon caninclude no rings, one ring, two rings, three rings, four rings, fiverings, or more.

Liquid and/or solid hydrocarbons and/or modified hydrocarbonssynthesized by the methods and devices provided herein are useful formany purposes. The liquid and/or solid hydrocarbon and/or modifiedhydrocarbon can be an isolated material or a mixture of materials. Aliquid and/or solid hydrocarbon and/or modified hydrocarbon providedherein may be suitable for purposes including, but not limited to fuels,adhesives, construction materials, chemical treatments, solvents,coatings, building blocks for chemical synthesis, preservatives,pharmaceuticals, personal care products, and refrigerants. A liquidand/or solid hydrocarbon and/or modified hydrocarbon provided herein maybe useful for polymerization to create materials useful as fabrics,packaging, furnishings, leisure devices including but not limited totoys, home maintenance and improvement technologies such as hoses, lawnfigurines, wall ornaments, fire extinguishers, HVAC equipment andcontrol devices, lighting, electrical infrastructure, clotheswashing anddishwashing equipment, flooring materials including padding, insulation,devices for cooking, and appliances.

It may be desirable to separate certain product stream materials fromother product stream materials. Any suitable method or methods ofseparation can be used. Persons of skill in the art have a number ofmethods and devices available to separate such materials. Numerous typesof chemical, physiochemical, and physical separation methods are knownto those of skill in the art, for example, including fractionaldistillation, affinity chromatography including, for example,centrifugal chromatography, thin-layer chromatography, gaschromatography and high pressure liquid chromatography; crystallization;electrophoresis; osmotic pressure-driven methods; and methods relying ondisparate solubility including, for example, solvent extraction, andtrituration. Separation techniques known to persons of skill in the artinclude adsorption, capillary electrophoresis, centrifugation, cyclonicseparation, chromatography, counter-current membrane separation,crystallization, decantation, demister (vapor), distillation, drying,electrophoresis, elutriation, evaporation, extraction (for example,liquid-liquid extraction), leaching, field flow fractionation,flotation, flocculation, filtration, fractional freezing, gravimetricseparation, precipitation, scrubbing, sedimentation, stripping, andsublimation. See, for example, Budhiraja, R. P., Separation Chemistry(New Age International Ltd, 2010). Distillation devices are describedin, for example, U.S. Pat. No. 5,271,810, U.S. Pat. No. 5,045,155, U.S.Pat. No. 4,234,391, and U.S. Pat. No. 9,194,623. Chromatographicseparation devices are described in, for example, U.S. 2007/0163960,U.S. 2008/0164193, U.S. 2011/0232373, U.S. Pat. No. 3,954,608, U.S. Pat.No. 4,139,458, and U.S. Pat. No. 4,678,570. Separation of a plurality ofproduct stream materials can be by fractional distillation according tothe knowledge of persons of skill in the art. Fractional distillationseparates chemical compounds boiling point by heating them to atemperature at which one or more fractions of the compound willvaporize. Compounds can be separated because a compound will be in thevapor phase only above its boiling temperature (at the pressure in thecolumn). Fractional distillation utilizes a fractionating column. Afractionating column includes nodules upon which condensation andreboiling can occur. Cycles of condensation and boiling allow eachcomponent to reach equilibrium, such that only compounds having aboiling point above the temperature of the mixture will remain in thevapor phase and reach the top of the column. Compounds in the vaporphase that reach the top of the fractionating column are condensed andthus separated from the other components of the mixture. As understoodby persons of skill in the art, compounds with very close boiling pointscan be separated using fractional distillation provided that afractionating column of sufficient length is used. Simple distillationcan also be used to separate compounds having substantially differentboiling points. A simple distillation column generally includes a smoothinner surface which is generally cylindrical in the interior dimension,although other shapes may be used. The separation efficiency can bedetermined by the number of theoretical plates. The Fenske equationprovides a method for determining the number of theoretical platesneeded for separation, for example, of two components:

$N = \frac{\log \lbrack {( \frac{X_{d}}{1 - X_{d}} )( \frac{1 - X_{b}}{X_{b}} )} \rbrack}{\log \mspace{14mu} \alpha_{avg}}$

Where: α_(avg) is the average relative volatility of the more volatilecomponent to the less volatile component; X_(d) is the mole fraction ofmore volatile component in the overhead distillate; X_(b) is the molefraction of the more volatile component in the bottoms liquid; and N isthe minimum number of theoretical plates or trays required at totalreflux. Distillation can be implemented as a batch distillation orcontinuous distillation.

Chemical derivatization, such as salt formation, esterification, oretherification of one or more species present in a mixture may beperformed in conjunction with one or more of the foregoing methods.

A separation can be used to obtain an isolated hydrocarbon or modifiedhydrocarbon as provided herein. An isolated hydrocarbon can include oneor more structural isomers. An isolated hydrocarbon can be characterizedby a range of molecular weight, by a degree of branching, or by a degreeof unsaturation, physical characteristic such as boiling point, degreeof unsaturation, degree of branching or a functional group present ineach member of the class, for example, alcohols, amides, carboxylicacids, olefins, and/or alkynes. In some embodiments, an isolated liquidhydrocarbon can be characterized by a range of boiling points.

In some embodiments, liquid and/or solid hydrocarbons in the productstream can be separated into individual compounds. Such separation canbe accomplished by any method provided herein, or known to persons ofskill in the art.

A compound produced by the methods and devices provided herein can bepurified by any suitable method. Numerous types of purification methodsare known to those of skill in the art, for example, includingdistillation, chromatography such as gas chromatography,crystallization, electrophoresis, osmotic pressure-driven methods andmethods relying on disparate solubility. Chemical derivatization of thespecies to be purified, or an impurity accompanying such a species, maybe performed in conjunction with one or more of the foregoing methods.For purification methods, see, for example, W. L. F. Armarego et al.,Purification of Laboratory Chemicals, (Butterworth-Heinemann, 2012).

In some embodiments, a compound is purified by gas chromatography.Persons of skill in the art possess the knowledge and resources toconduct gas chromatography. Generally, gas chromatography includes thesteps of vaporizing a sample by applying heat and/or vacuum, and passingthe vaporized sample through a column. A column can be a tube containinga stationary phase, or packing, of liquid or polymer on an inert solidsupport. A gas chromatography column will generally include a stationaryphase comprising a material selected to interact with components of thevaporized sample. Due to disparate affinity of each component with thepacking, each component has a different retention time in the column.For a study on the separation of hydrocarbons by gas chromatography, seefor example, Singh, B. N., et al., Separation of light hydrocarbons bygas chromatography using serpentine as stationary phase, Indian J. ofChem. Tech. (November 2004), Vol. 11, pp. 793-796, which is incorporatedherein by reference in the entirety.

In some embodiments, a liquid and/or solid hydrocarbon or modifiedhydrocarbon synthesized by a method or device provided herein can besubjected to a plurality of isolation and/or purification proceduresprovided herein and/or known to those of skill in the art. For example,a liquid hydrocarbon can be isolated by distillation, and subsequentlypurified by gas chromatography to provide a substantially pure compoundprovided herein, such as a compound of Formula (I), where substantiallypure means that the compound is free from gas-chromatography detectableimpurities. The compound can also be a purified compound, wherein amixture containing the compound is subjected to steps to removeextraneous compounds to yield an enriched product containing at least70%, 80%, 90%, 95%, 98%, 99%, 99.5%, or 99.9% of the compound.

Example 1

Power supply frequencies applied to the electrode of device 100 werevaried using propane as the gas phase hydrocarbon, to produce liquidhydrocarbons and solid hydrocarbons, as indicated in FIGS. 2A and 2B.With regard to the conversion to liquid, referring to FIG. 2B, it isshown that various percentages of different liquid molecules are formedfrom the hydrocarbon gas at discrete electrical frequencies supplied tothe electrode 2. More specifically, FIG. 2B shows the data as obtainedfrom gas chromatography (GC) and shows that the 100%<C8 indicates thatmost of the liquid species in this group will be recognized on the GCbefore the C8 standard would be detected. Likewise for the <C10and >C10. The material being detected between C8 and C10 are notnecessarily a specific hydrocarbon, but are chemicals that are detectedby the GC after the C8 standard and before the C10 standard.Materials >C10 are species that pass through the GC and are detectedafter the C10 standard. Thus, there may be some C6, or other chainlength, molecules, but the molecular arrangement gives them a vaporpressure higher than the C10 standard. There are possibly hundreds ofmolecular species that can be formed which will fall into the variousgroups. It should be noted that at each applied frequency, the totalpercentage of the converted liquid sums to approximately 100%.

Example 2

A device of FIGS. 1 and 3-8 and as provided herein was operated at thefollowing parameters: 440 Hz; 24,600 VAC sec voltage; atmosphericpressure; and ambient temperature. The gas phase hydrocarbon input waspropane.

Four (4) samples were collected. Sample 1 was a solvent blank containingonly acetone. Sample 2 was solid residue collected from the reactorwall, diluted. Sample 3 was liquid product stream, diluted. Sample 4 wasneat liquid product stream. Descriptions of samples S1 to S4 areprovided in Table 2.

Gas chromatography was performed using an Agilent™ HP-5 column, having a30 m length, a 0.25 mm inner diameter and a split ratio of 50:1. Thetemperature program was as follows: temperature was held at 40° C. for 3min; 40-200° C. at a heating rate of 5° C./min; then 200-280° C. at aheating rate of 10° C./min. Mass spectrometry results for sample S4,using a best fit model, are provided in Table 3. Gas chromatographyresults for sample S4 are provided in Table 4.

TABLE 2 Sample # Description S1 Acetone blank S2 Solids residue fromreactor walls, diluted in acetone S3 Liquid product stream, diluted inacetone S4 Liquid product stream, neat

TABLE 3 Retention Reverse Time Mass/ Match Match NIST (min) SpectralMatch Formula Factor Factor Prob. 1.185 Propane C3H8 973 973 95% 1.217Isobutane C4H10 927 927 80% 1.241 Butane C4H10 886 886 73% 1.329 Butane,2-methyl- C5H12 956 959 89% 1.369 Acetone C3H6O 865 865 61% 1.377Isopropyl Alcohol C3H8O 720 767 17% 1.602 Pentane, 2-methyl- C6H14 916925 62% 1.762 n-Hexane C6H14 925 933 73% 2.034 Butane, 2,2,3-trimethyl-C7H16 914 914 45% 2.322 Hexane, 2-methyl- C7H16 887 901 48% 2.362Pentane, 2,3-dimethyl- C7H16 910 910 47% 2.435 Hexane, 3-methyl- C7H16949 949 62% 3.372 Hexane, 2,4-dimethyl- C8H18 926 926 41% 3.572 Hexane,3,3-dimethyl- C8H18 914 915 38% 3.956 Pentane, 2,3,3-trimethyl- C8H18914 915 53% 4.092 Hexane, 2,3-dimethyl- C8H18 920 922 48% 4.478 Heptane,3-methyl- C8H18 949 957 42% 5.41 Octane C8H18 6.015 Hexane,2,3,5-trimethyl- C9H20 937 938 42% 7.000 Hexane, 2,3,3-trimethyl- C9H20890 895 16% 7.833 Heptane, 2,3-dimethyl- C9H20 863 865 29% 8.161 Octane,4-methyl- C9H20 902 905 36% 8.481 Octane, 3-methyl- C9H20 855 874 11%8.649 Heptane, 2,2,4-trimethyl- C10H22 884 916 36% 9.090 Heptane,2,4,6-trimethyl- C10H22 845 859  8% 9.710 Nonane C9H20 9.7394,4-Dimethyl octane C10H22 874 877 22% 10.403 Heptane, 2,3,5-trimethyl-C10H22 857 885 32% 10.836 Octane, 2,5-dimethyl- C10H22 856 857 21% 11.18Heptane, 2,3,6-trimethyl C10H22 853 855  7% 11.717 Heptane,2,3,5-trimethyl- C10H22 842 863 17% 12.149 Nonane, 4-methyl C11H24 870881  9% 13.054 Octane, 2,3,3-trimethyl- C11H24 862 889 13% 14.09 DecaneC10H22 14.552 Octane, C12H26 835 857 14% 3,4,5,6-tetramethyl- 14.952Nonane, 3-methyl- C10H22 842 878 10% 15.361 Decane, 3,6-dimethyl- C12H26848 856 12% 16.674 Decane, 2,5,9-trimethyl- C13H28 794 844  6% 17.451Octane, C12H26 838 872 11% 2,3,6,7-tetramethyl- 18.18 Undecane C11H2419.293 Undecane, 5,7-dimethyl- C13H28 872 882 27% 21.440 Decane,2,3,6-trimethyl- C13H28 801 844  8% 21.970 Dodecane C12H26

TABLE 4 Retention Mass/ Time (min) Spectral Match Formula Area Percent1.185 Propane C3H8 13674744 0.17% 1.217 Isobutane C4H10 14037704 0.17%1.241 Butane C4H10 28137338 0.35% 1.329 Butane, 2-methyl- C5H12 709733670.88% 1.369 Acetone C3H6O 240687131 2.97% 1.377 Isopropyl Alcohol C3H8O360127348 4.44% 1.602 Pentane, 2-methyl- C6H14 200729040 2.47% 1.762n-Hexane C6H14 132909430 1.64% 2.034 Butane, 2,2,3-trimethyl- C7H16192509342 2.37% 2.322 Hexane, 2-methyl- C7H16 260088595 3.21% 2.362Pentane, 2,3-dimethyl- C7H16 214293317 2.64% 2.435 Hexane, 3-methyl-C7H16 118247949 1.46% 3.372 Hexane, 2,4-dimethyl- C8H18 277742629 3.42%3.572 Hexane, 3,3-dimethyl- C8H18 411076226 5.07% 3.956 Pentane,2,3,3-trimethyl- C8H18 427008978 5.26% 4.092 Hexane, 2,3-dimethyl- C8H18270109110 3.33% 6.015 Hexane, 2,3,5-trimethyl- C9H20 554883957 6.84%7.000 Hexane, 2,3,3-trimethyl- C9H20 765085303 9.43% 7.833 Heptane,2,3-dimethyl- C9H20 395838714 4.88% 8.161 Octane, 4-methyl- C9H20317981185 3.92% 8.481 Octane, 3-methyl- C9H20 216602963 2.67% 8.649Heptane, 2,2,4-trimethyl- C10H22 150153351 1.85% 9.090 Octane,2,4,6-trimethyl- C11H24 144791181 1.79% 9.739 4,4-Dimethyl octane C10H22265381045 3.27% 10.403 Heptane, 2,3,5-trimethyl- C10H22 285161227 3.52%10.836 Octane, 2,5-dimethyl- C10H22 112618597 1.39% 11.18 Hexane, C9H20137825010 1.70% 4-ethyl-2-methyl- 11.717 Heptane, 2,3,5-trimethyl-C10H22 265334471 3.27% 12.149 Undecane, 2,6-dimethyl- C13H28 1382723021.70% 13.054 Octane, 2,3,3-trimethyl- C11H24 153331788 1.89% 14.552Octane, C12H26 80912092 1.00% 3,4,5,6-tetramethyl- 14.952 Nonane,3-methyl- C10H22 129050313 1.59% 15.361 Decane, 3,6-dimethyl- C12H26210633710 2.60% 16.674 Decane, 2,5,9-trimethyl- C13H28 65315712 0.81%17.451 Octane, C12H26 325298855 4.01% 2,3,6,7-tetramethyl- 19.293Undecane, 5,7-dimethyl- C13H28 124689436 1.54% 21.440 Decane,2,3,6-trimethyl- C13H28 39714150 0.49% Total 8111227610

Example 3

A device according to FIG. 1 having a longitudinal electrodeconfiguration according to FIG. 7 was operated at the followingparameters: 440 Hz; 24,600 VAC sec voltage; atmospheric pressure; andambient temperature. The gas phase hydrocarbon input was propane. Aproduct stream sample S5 was collected and analyzed by gaschromatography. The GC output for sample S5 is provided in FIG. 14A.Compounds identified in the GC chromatogram for sample S5 are providedin Table 5.

TABLE 5 RT Area Name 1.4254 57.8044 Acetone 1.7951 11.8393 Acetone4.6696 2.8051 Hexane, 2,3,5-trimethyl- 4.9064 1.953 Heptane,2,4-dimethyl- 5.0464 1.7889 Trichloroacetic acid, 4-methylpentyl ester5.1648 3.5609 Pentane, 3-ethyl-2,4-dimethyl- 5.6493 3.5684 Pentane,3-ethyl-2,4-dimethyl- 5.8861 3.598 Octane, 4-methyl- 6.245 2.2575 Allylmethallyl ether 8.1111 10.8245 Octane, 2,5,6-trimethyl-

A second experiment under conditions indicated above for Example 3 wasperformed. A product stream sample S6 was collected and analyzed by gaschromatography. The GC output for sample S6 is provided in FIG. 14B.Compounds identified in the GC chromatogram for sample S6 are providedin Table 6.

TABLE 6 RT Area Name 1.4473 40.4976 Acetone 1.7021 10.3522 Acetone 3.2132.8166 3-Pentanol, 2,2-dimethyl- 3.8948 2.164 Heptane, 3-methyl- 4.72386.9858 Hexane, 2,3,5-trimethyl- 4.8853 2.4631 Heptane, 2,4-dimethyl-5.2369 14.0658 Hexane, 2,3,5-trimethyl- 5.6353 3.289 Pentane,3-ethyl-2,4-dimethyl- 5.8757 2.9051 Octane, 4-methyl- 6.231 1.64551-Octanol, 3,7-dimethyl-, (S)- 8.1258 8.9646 Nonane

While various embodiments of the invention have been described above, itshould be understood that they have been presented by way of exampleonly, and not by way of limitation. Likewise, the various diagrams maydepict an example architectural or other configuration for thedisclosure, which is done to aid in understanding the features andfunctionality that can be included in the disclosure. The disclosure isnot restricted to the illustrated example architectures orconfigurations, but can be implemented using a variety of alternativearchitectures and configurations. Additionally, although the disclosureis described above in terms of various exemplary embodiments andimplementations, it should be understood that the various features andfunctionality described in one or more of the individual embodiments arenot limited in their applicability to the particular embodiment withwhich they are described. They instead can be applied, alone or in somecombination, to one or more of the other embodiments of the disclosure,whether or not such embodiments are described, and whether or not suchfeatures are presented as being a part of a described embodiment. Thusthe breadth and scope of the present disclosure should not be limited byany of the above-described exemplary embodiments.

It will be appreciated that, for clarity purposes, the above descriptionhas described embodiments with reference to different functional units.However, it will be apparent that any suitable distribution offunctionality between different functional units may be used withoutdetracting from the invention. For example, functionality illustrated tobe performed by separate computing devices may be performed by the samecomputing device. Likewise, functionality illustrated to be performed bya single computing device may be distributed amongst several computingdevices. Hence, references to specific functional units are only to beseen as references to suitable means for providing the describedfunctionality, rather than indicative of a strict logical or physicalstructure or organization.

Embodiments of the present disclosure are described above and below withreference to flowchart illustrations of methods, apparatus, and computerprogram products. It will be understood that each block of the flowchartillustrations, and combinations of blocks in the flowchartillustrations, can be implemented by execution of computer programinstructions. These computer program instructions may be loaded onto acomputer or other programmable data processing apparatus (such as acontroller, microcontroller, microprocessor or the like) in a sensorelectronics system to produce a machine, such that the instructionswhich execute on the computer or other programmable data processingapparatus create instructions for implementing the functions specifiedin the flowchart block or blocks. These computer program instructionsmay also be stored in a computer-readable memory that can direct acomputer or other programmable data processing apparatus to function ina particular manner, such that the instructions stored in thecomputer-readable memory produce an article of manufacture includinginstructions which implement the function specified in the flowchartblock or blocks. The computer program instructions may also be loadedonto a computer or other programmable data processing apparatus to causea series of operational steps to be performed on the computer or otherprogrammable apparatus to produce a computer implemented process suchthat the instructions which execute on the computer or otherprogrammable apparatus provide steps for implementing the functionsspecified in the flowchart block or blocks presented herein.

All references cited herein are incorporated herein by reference intheir entirety. To the extent publications and patents or patentapplications incorporated by reference contradict the disclosurecontained in the specification, the specification is intended tosupersede and/or take precedence over any such contradictory material.

Unless otherwise defined, all terms (including technical and scientificterms) are to be given their ordinary and customary meaning to a personof ordinary skill in the art, and are not to be limited to a special orcustomized meaning unless expressly so defined herein. It should benoted that the use of particular terminology when describing certainfeatures or aspects of the disclosure should not be taken to imply thatthe terminology is being re-defined herein to be restricted to includeany specific characteristics of the features or aspects of thedisclosure with which that terminology is associated. Terms and phrasesused in this application, and variations thereof, especially in theappended claims, unless otherwise expressly stated, should be construedas open ended as opposed to limiting. As examples of the foregoing, theterm ‘including’ should be read to mean ‘including, without limitation,’‘including but not limited to,’ or the like; the term ‘comprising’ asused herein is synonymous with ‘including,’ ‘containing,’ or‘characterized by,’ and is inclusive or open-ended and does not excludeadditional, unrecited elements or method steps; the term ‘having’ shouldbe interpreted as ‘having at least;’ the term ‘includes’ should beinterpreted as ‘includes but is not limited to;’ the term ‘example’ isused to provide exemplary instances of the item in discussion, not anexhaustive or limiting list thereof; adjectives such as ‘known’,‘normal’, ‘standard’, and terms of similar meaning should not beconstrued as limiting the item described to a given time period or to anitem available as of a given time, but instead should be read toencompass known, normal, or standard technologies that may be availableor known now or at any time in the future; and use of terms like‘preferably,’ ‘preferred,’ ‘desired,’ or ‘desirable,’ and words ofsimilar meaning should not be understood as implying that certainfeatures are critical, essential, or even important to the structure orfunction of the invention, but instead as merely intended to highlightalternative or additional features that may or may not be utilized in aparticular embodiment of the invention. Likewise, a group of itemslinked with the conjunction ‘and’ should not be read as requiring thateach and every one of those items be present in the grouping, but rathershould be read as ‘and/or’ unless expressly stated otherwise. Similarly,a group of items linked with the conjunction ‘or’ should not be read asrequiring mutual exclusivity among that group, but rather should be readas ‘and/or’ unless expressly stated otherwise.

Where a range of values is provided, it is understood that the upper andlower limit, and each intervening value between the upper and lowerlimit of the range is encompassed within the embodiments.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity. The indefinite article “a” or “an” does not exclude aplurality. A single processor or other unit may fulfill the functions ofseveral items recited in the claims. The mere fact that certain measuresare recited in mutually different dependent claims does not indicatethat a combination of these measures cannot be used to advantage. Anyreference signs in the claims should not be construed as limiting thescope.

It will be further understood by those within the art that if a specificnumber of an introduced claim recitation is intended, such an intentwill be explicitly recited in the claim, and in the absence of suchrecitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should typically be interpreted to mean “atleast one” or “one or more”); the same holds true for the use ofdefinite articles used to introduce claim recitations. In addition, evenif a specific number of an introduced claim recitation is explicitlyrecited, those skilled in the art will recognize that such recitationshould typically be interpreted to mean at least the recited number(e.g., the bare recitation of “two recitations,” without othermodifiers, typically means at least two recitations, or two or morerecitations). Furthermore, in those instances where a conventionanalogous to “at least one of A, B, and C, etc.” is used, in generalsuch a construction is intended in the sense one having skill in the artwould understand the convention (e.g., “a system having at least one ofA, B, and C” would include but not be limited to systems that have Aalone, B alone, C alone, A and B together, A and C together, B and Ctogether, and/or A, B, and C together, etc.). In those instances where aconvention analogous to “at least one of A, B, or C, etc.” is used, ingeneral such a construction is intended in the sense one having skill inthe art would understand the convention (e.g., “a system having at leastone of A, B, or C” would include but not be limited to systems that haveA alone, B alone, C alone, A and B together, A and C together, B and Ctogether, and/or A, B, and C together, etc.). It will be furtherunderstood by those within the art that virtually any disjunctive wordand/or phrase presenting two or more alternative terms, whether in thedescription, claims, or drawings, should be understood to contemplatethe possibilities of including one of the terms, either of the terms, orboth terms. For example, the phrase “A or B” will be understood toinclude the possibilities of “A” or “B” or “A and B.”

All numbers expressing quantities of ingredients, reaction conditions,and so forth used in the specification are to be understood as beingmodified in all instances by the term ‘about.’ Accordingly, unlessindicated to the contrary, the numerical parameters set forth herein areapproximations that may vary depending upon the desired propertiessought to be obtained. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of anyclaims in any application claiming priority to the present application,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding approaches.

Furthermore, although the foregoing has been described in some detail byway of illustrations and examples for purposes of clarity andunderstanding, it is apparent to those skilled in the art that certainchanges and modifications may be practiced. Therefore, the descriptionand examples should not be construed as limiting the scope of theinvention to the specific embodiments and examples described herein, butrather to also cover all modification and alternatives coming with thetrue scope and spirit of the invention.

What is claimed is:
 1. A method for synthesizing a hydrocarbon,comprising: providing a gas phase hydrocarbon; and subjecting the gasphase hydrocarbon to a plasma created by an electrostatic field, wherebya first hydrocarbon is obtained, wherein the first hydrocarbon isselected from the group consisting of butane, 2-methyl-butane,2-methyl-pentane, n-hexane, 2,2,3-trimethyl-butane, 2-methyl-hexane,2,3-dimethyl-pentane, 3-methyl-hexane, 2,4-dimethyl-hexane,3,3-dimethyl-hexane, 2,3,3-trimethyl-pentane, 2,3-dimethyl-hexane,3-methyl-heptane, 2,3,5-trimethyl-hexane, 2,3,3-trimethyl-hexane,2,3-dimethyl-heptane, 2,2,4-trimethyl-heptane, 2,4,6-trimethyl-heptane,4-ethyl-2-methyl-hexane, 2,3,5-trimethyl-heptane,2,3,6-trimethyl-heptane, 2,3,5-trimethyl-heptane, octane,4-methyl-octane, 3-methyl-octane, 2,4,6-trimethyl-octane,4,4-dimethyl-octane, 2,5-dimethyl-octane, 2,3,3-trimethyl-octane,3,4,5,6-tetramethyl-octane, 2,3,6,7-tetramethyl-octane, nonane,3-methyl-nonane, 4-methyl-nonane, 3-methyl-nonane, decane,3,6-dimethyl-decane, 2,3,6-trimethyl-decane, 2,5,9-trimethyl-decane,undecane, 2,6-dimethyl-undecane, 5,7-dimethyl-undecane, dodecane,2,3,3-trimethyl-pentane, 3,3-dimethyl-hexane, 2,3-dimethyl-heptane,4-methyl-octane, 3-methyl-octane, and 3-methyl-nonane.
 2. The method ofclaim 1, wherein the first hydrocarbon is selected from the groupconsisting of butane, 2-methyl-butane, 2-methyl-pentane, n-hexane,2,2,3-trimethyl-butane, 2-methyl-hexane, 2,3-dimethyl-pentane,3-methyl-hexane, 2,4-dimethyl-hexane, 3,3-dimethyl-hexane,2,3,3-trimethyl-pentane, 2,3-dimethyl-hexane, 3-methyl-heptane,2,3,5-trimethyl-hexane, 2,3,3-trimethyl-hexane, 2,3-dimethyl-heptane,2,2,4-trimethyl-heptane, 2,4,6-trimethyl-heptane,4-ethyl-2-methyl-hexane, 2,3,5-trimethyl-heptane,2,3,6-trimethyl-heptane, and 2,3,5-trimethyl-heptane.
 3. The method ofclaim 1, wherein the first hydrocarbon is selected from the groupconsisting of octane, 4-methyl-octane, 3-methyl-octane,2,4,6-trimethyl-octane, 4,4-dimethyl-octane, 2,5-dimethyl-octane,2,3,3-trimethyl-octane, 3,4,5,6-tetramethyl-octane,2,3,6,7-tetramethyl-octane, nonane, 3-methyl-nonane, 4-methyl-nonane,3-methyl-nonane, decane, 3,6-dimethyl-decane, 2,3,6-trimethyl-decane,and 2,5,9-trimethyl-decane.
 4. The method of claim 1, wherein the firsthydrocarbon is selected from the group consisting of undecane,2,6-dimethyl-undecane, 5,7-dimethyl-undecane, and dodecane.
 5. Themethod of claim 1, wherein the first hydrocarbon is selected from thegroup consisting of, 2,3,3-trimethyl-pentane, 3,3-dimethyl-hexane,2,3-dimethyl-heptane, 4-methyl-octane, 3-methyl-octane, and3-methyl-nonane.
 6. The method of claim 1, wherein the first hydrocarbonis obtained as a mixture with a second hydrocarbon different from thefirst hydrocarbon, wherein the second hydrocarbon is selected from thegroup consisting of butane, 2-methyl-butane, 2-methyl-pentane, n-hexane,2,2,3-trimethyl-butane, 2-methyl-hexane, 2,3-dimethyl-pentane,3-methyl-hexane, 2,4-dimethyl-hexane, 3,3-dimethyl-hexane,2,3,3-trimethyl-pentane, 2,3-dimethyl-hexane, 3-methyl-heptane, octane,2,3,5-trimethyl-hexane, 2,3,3-trimethyl-hexane, 2,3-dimethyl-heptane,4-methyl-octane, 3-methyl-octane, 2,4,6-trimethyl-octane,2,2,4-trimethyl-heptane, 2,4,6-trimethyl-heptane, nonane,4-ethyl-2-methyl-hexane, 4,4-dimethyl-octane, 2,3,5-trimethyl-heptane,2,5-dimethyl-octane, 2,3,6-trimethyl-heptane, 2,3,5-trimethyl-heptane,3-methyl-nonane, 4-methyl-nonane, 2,3,3-trimethyl-octane, decane,3,4,5,6-tetramethyl-octane, 3-methyl-nonane, 3,6-dimethyl-decane,2,5,9-trimethyl-decane, 2,3,6,7-tetramethyl-octane, undecane,2,6-dimethyl-undecane, 5,7-dimethyl-undecane, 2,3,6-trimethyl-decane,and dodecane.
 7. The method of claim 1, further comprising condensingthe first hydrocarbon to yield a liquid hydrocarbon.
 8. The method ofclaim 1, wherein the electrostatic field is an oscillating field.
 9. Themethod of claim 8, wherein the field oscillates at a frequency from 60to 1000 Hz.
 10. The method of claim 8, wherein the field oscillates at afrequency from 300 to 600 Hz.
 11. The method of claim 1, wherein theelectrostatic field is from 1000 to 100,000 volts.
 12. The method ofclaim 1, wherein the electrostatic field is from 10,000 to 50,000 volts.13. The method of claim 1, wherein subjecting to a plasma is conductedat ambient temperature.
 14. The method of claim 1, wherein subjecting toa plasma is conducted at a pressure of from atmospheric pressure to 100PSIG.
 15. The method of claim 1, wherein subjecting to a plasma isconducted at atmospheric pressure.
 16. The method of claim 1, whereinthe gas phase hydrocarbon is selected from the group consisting ofmethane, ethane, n-propane, isopropane, n-butane, isobutane, ethylene,propylene, butylene, acetylene, methylacetylene, ethylacetylene, andmixtures thereof.
 17. The method of claim 16, wherein the gas phasehydrocarbon is n-propane.
 18. The method of claim 1, further comprisingisolating the first hydrocarbon.
 19. A device for propagating moleculargrowth of hydrocarbons, comprising: an electrically charged or groundedvessel having an inlet, an outlet and an electrode within the vessel;and a power supply coupled through the vessel to the electrode.
 20. Thedevice of claim 19, wherein the vessel comprises more than oneelectrode.
 21. The device of claim 19, wherein the vessel comprises 1+nelectrodes coupled to the power supply and n grounded electrodes, wheren is an integer ≥1.
 22. The device of claim 19, wherein the power supplyis configured to provide a variable frequency source of power.
 23. Thedevice of claim 19, wherein the power supply is configured to provide avariable voltage supply of power.
 24. The device of claim 19, whereinthe power supply is configured to provide both a variable frequencysupply of power and a variable voltage supply of power.
 25. The deviceof claim 19, wherein the outlet of the vessel is located at a levelbelow a liquid gas interface of the vessel.